Mesoporous HBeta zeolite obtained: Via zeolitic dissolution-recrystallization successive treatment for vapor-phase Doebner-Von Miller reaction to quinolines

Article abstract of DOI:10.1039/d0nj04539j

A reassembled HBeta zeolite (HBeta-Ct) was obtained via zeolitic dissolution-recrystallization successive treatment, and characterized by means of XRD, FT-IR, SEM, TEM, N2 adsorption-desorption as well as NH3-TPD techniques. The characterization results manifested that the HBeta-Ct zeolite possessed more mesopores and less acid than the parent one. Catalyst activities of the parent and reassembled HBeta catalysts were investigated in detail in the vapor-phase Doebner-Von Miller reaction to quinolines. The results demonstrated that the reassembled HBeta zeolite showed enhanced catalyst stability and improved anti-alkylation ability. This is probably due to the existence of mesopores on the catalyst which strengthened the diffusion of bulky products from pore channels in the zeolite. Meanwhile, the decreased acid amount over the catalyst can also retard the alkylation process to generate alkylquinolines as well as the acid-induced polymerization reaction to form coke. Besides, the HBeta-Ct catalyst also exhibited good regenerability in the Doebner-Von Miller reaction. This journal is

Full text of DOI:10.1039/d0nj04539j

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: A. Li, C. Luo, F.
WU, S. Zheng, L. Li, J. Zhang, L. Chen, K. Liu and C. Zhou, New J. Chem., 2020, DOI:
1
0.1039/D0NJ04539J.
Volume 42
Number
March 2018
Pages 3963-4776
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
6
21
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Page 1 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
Mesoporous HBeta Zeolite via Zeolitic Dissolution-
Recrystallization Successive Treatment for Vapor-Phase
Doebner-Von Miller Reaction to Quinolines
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
An Li a#*, CaiWu Luo , Fen Wu , ShuQin Zheng , LiJun Li , JianCe Zhang , Liang Chen
b#
a#
a
a
a
a, Kun Liu a* and Congshan Zhou a*
a
Province Key Laboratory for Fine Petrochemical Catalysis and Separation, College of
Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang,
Hunan, 414000, P. R. China.
b
School of Environmental Protection and Safety Engineering, University of South China,
Hengyang, Hunan 421001, China.
#
Coauthors equally contributed to this work.
*
Corresponding author. Email: anleechn@hotmail.com
zhoucongsh@126.com.
＆
liukun328@126.com
＆
1

New Journal of Chemistry
Page 2 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
ABSTRACT
The reassembled HBeta zeolite (HBeta-Ct) was obtained via zeolitic
dissolution-recrystallization successive treatment, and characterized by means of
XRD, FT-IR, SEM, TEM, N adsorption-desorption as well as NH -TPD techniques.
2
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The characterization results manifested that the HBeta-Ct zeolite possessed more
mesopores and less acid amount than the parent one. Catalyst activities of the parent
and reassembled HBeta catalysts were investigated detailedly in vapor-phase
Doebner-Von Miller reaction to quinolines. The results demonstrated that the
reassembled HBeta zeolite showed enhanced stability of catalyst and improved
ability of anti-alkylation. This is probably due to the existence of mesopores on
catalyst which strengthened the diffusion of bulky products from pore channels in
zeolite. Meanwhile, the decreased acid amount over catalyst can also retard the
alkylation process to generate alkylquinolines as well as the acid-induced
polymerization reaction to form the coking. Besides, the HBeta-Ct catalyst also
exhibited good regenerability in Doebner-Von Miller reaction.
Keywords: recrystallization, Doebner-Von Miller reaction, acrolein diethyl acetal,
quinolines, alkylation
2

Page 3 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
1
Introduction
Quinoline derivatives are important nitrogen-containing heterocyclic compounds
used extensively in drug design.1-3 Doebner-Von Miller reaction(DVM) is one of the
most effective synthetic methods to produce quinoline derivatives.4-9 Generally, DVM
reaction employs arylamine and α, β-unsaturated aldehydes as starting materials, via
michael addition of aniline and unsaturated ketone under acidic conditions and
subsequent cyclization to dihydroquinoline. Although being attractive due to its
straightforward workup procedures, the DVM method always is conducted via
conventional liquid-phase means, which suffer from long reaction time, volatile
organic solvents, complicated catalyst separation and etc.6, 7, 10, 11 For example, Cowen
et al. reported the liquid-phase DVM reaction using acrolein diethyl acetals and
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
aniline as substrates ; and satisfied yield of quinoline was achieved under organic
solvent conditions for 24 h with corrosive acid as catalyst. Thus, in order to avoid
mentioned-above drawbacks, the further development of vapor-phase DVM reaction
to quinolines is of great interest and still desirable.
Zeolites have been widely employed as heterogeneous catalysts in oil refining,
gas absorption and fine chemicals, because of their high surface area, uniform pore
sizes, excellent hydrothermal stability and adjustable acid sites.12-15 Interestingly, Beta
zeolite possesses more appropriate pore size (0.56×0.56 nm and 0.66×0.67 nm) to
match with quinolines molecule size than the other zeolites, and it was certified to be
a high-activity catalyst for the gas-phase reaction to synthesize quinolines.16-18
.
However, the property of single micropores of Beta zeolite easily imposes diffusion
limitation of bulky quinolines molecule in zeolitic pore channels, thereby leading to
serious catalyst deactivation. Several literatures revealed that pure microporous Beta
catalyst showed low catalytic stability in the quinolines` vapor-phase synthetic
reactions.17-19 Thus, in order to overcome diffusional limitation within zeolites,
creating added hierarchically pores on zeolite provides an alternative strategy to
promote faster diffusion of bulky reactants and products in pore channels.
In recent years, mesoporous Beta zeolite has been widely applied in numerous
bulky molecular reactions, such as, alkylation, conversion of synthesis Gas,
3

New Journal of Chemistry
Page 4 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
isomerization, benzoylation, quinolines synthesis and etc.20-26 The catalytic evaluation
results manifested that mesoporous zeolites exhibited superior catalytic activity and
stability than corresponding microporous one. Mesoporous Beta zeolite could be
prepared by various tactics, such as, acid/alkaline post-treatment, hard templates and
soft templates method, recrystallization of amorphous zeolitic seeds or silicon
aluminum source, dry-gel conversion and etc.27-36 Among these methods, zeolitic
recrystallization treatment was pursued to gain mesoporous Beta zeolite, via alkaline
treatment of zeolite to form amorphous silica-alumina sources and subsequent
recrystallization with template agents. Zhang et. al. reported that the Beta/MCM-41
zeolite composite could be obtained via alkali-treated zeolite and subsequent
DOI: 10.1039/D0NJ04539J
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
30
recrystallization with CTAB as template agent at alkaline environment.
Interestingly, Shi et al revealed that recrystallization process existed competition
balance between crystallization of zeolite and self-assembly of mesoporous, and the
final morphology of hierarchical materials could be regulated via adjusting the pH of
3
7
crystallization system. As a result, the hierarchical catalyst possessed a stepwise
distributed pore structure and showed enhanced activity and sulfur tolerance in
hydrogenation reaction of bulky naphthalene.30
Herein, in this work, the parent HBeta zeolite was improved via zeolitic
dissolution-recrystallization successive treatment, and the treated HBeta zeolite
(
named HBeta-Ct) was used as the green solid-acid catalyst for vapor-phase
Doebner-Von Miller reaction to quinolines. The activity and stability of catalysts were
systematically investigated; and the relationship between texture and performance of
catalysts was also discussed in this paper.
2. Experimental
2
.1. Materials
All the chemicals, including acrolein dimethyl acetal, acrolein diethyl acetal,
aniline, ethanol, cetyl trimethyl ammonium bromide, ammonium nitrate, acetic acid
sodium hydroxide and so on, were purchased from Sinopharm Chemical Reagent
Company and had analytic purity. The parent zeolites, including HY(Si/Al=6),
4

Page 5 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
HUSY(Si/Al=10), HZSM-5(Si/Al=25), HBeta(Si/Al=25), were supplied by Nankai
University Catalyst Factory.
2
.2. Catalyst Preparation
2
.2.1. Preparation of the H-formed HBeta zeolite
The H-formed Beta zeolite was treated via ion-exchange method. Firstly, the
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
parent Beta zeolite was added into the 1.0 M NH NO solution to reflux 4h with
4
3
strong stirring at 90 °C. Afterwards, the obtained slurries were filtrated, and dried one
night at 120 °C. The above processes of ion-exchange to drying were repetitively
operated three times. After that, the dried solid was calcined at 550 °C for 4 h, and the
thus-obtained catalyst was denoted as HBeta.
2
.2.2. The treatment of HBeta zeolite via dissolution-recrystallization processes
The typical zeolitic dissolution-recrystallization successive treatment procedure,
3
0
according to the previous literature, is described as follows: The prepared HBeta
zeolite powder was added to 1.85M solution of sodium hydroxide, and then refluxed
for 70 min at 40 °C under vigorous stirring. After that, aqueous solution of cetyl
trimethyl ammonium bromide (8.5g CTAB, 14.5wt%) was dropt into the above
suspension under strong stirring, and the pH was adjusted to 11.1~11.3 using acetic
acid. After stirring for 0.5 h, the obtained slurry was transferred into a teflon-coated
o
stainless-steel autoclave and crystallization treated for 12-36 h at 120 C. Then, the
precipiated product was obtained via filtering, washing, dried one night at 120 °C, and
calcined at 550 °C for 4 h. Finally, the catalyst was obtained through the as-above
ion-exchange process and re-calcined 4 h at 550 °C. The as-prepared catalysts
undergoing crystallization time for 12 h, 24 h and 36 h were named as HBeta-Ct,
HBeta-Ct-24 and HBeta-Ct-36, respectively.
2
.3. Catalysts Characterization
X-ray diffraction (XRD) spectra of catalysts were recorded by a Bruker D8
diffraction instrument. Operating scanning voltage was 40 kV and scanning current
was 40 mA using Cu Kα ray (λ=1.54187 Å), scanning speed was conducted at 0.2 s
and scanning step conducted at 0.02o.
Fourier transform infrared (FT-IR) spectra of catalysts were performed on a
5

New Journal of Chemistry
Page 6 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
Varian 3100 spectrometer. The sample was thoroughly mixed with KBr and then
placed into sample holder to install in spectrometer cavity. Spectrums were measured
-1
using scanning number of 32 with the resolution at 2 cm .
Scanning electron microscope (SEM) images were measured on Hitachi S4800
apparatus with accelerating voltage at 5 kV. Prior to measurement, the samples were
initially adequately dispersed in ethanol, and then dropped onto the silicon chip.
Transmission electron microscope (TEM) images were tested using JEM-2100F
instrument. The accelerating voltage was set at 200 kV. Before testing, samples were
dispersed fully in ethanol via ultrasonic process, and doped onto the copper grid.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N adsorption-desorption measurements were performed on Quantachrome
2
Autosorb-1 instrument. The sample was firstly degassed for 12 hours with vacuum
-8
condition of 10 Torr at 300 °C, and then measured the adsorption-desorption
isothermals. The multipoint BET equation analysis method was used to investigate
specific surface area. The “t-plot” analysis method was employed to calculate
microporous area as well as volume, and the BJH analysis methods were applied to
estimate the mesopore size distribution using adsorption branch of isotherms.
Temperature-programmed desorption of ammonia (NH -TPD) was performed on
3
Autochem II 2920 apparatus. Before NH adsorption, the samples were treated at
3
4
00 °C in the flow of He (60ml/min) for 0.5 h. Later on, the sample began to adsorb
NH up to saturation with 10 vol.% NH in the flow of He (50 ml/min). Then,
3
3
physically adsorbed NH was thoroughly purged for 1 using He flow at 100 °C.
3
Finally, ammonia on sample was desorbed in the range 100~800 °C with 10 °C/min
heating rates.
Thermogravimetry (TG) measurements were performed on Diamond apparatus.
The deactivated catalysts were heated from 25 °C to 800 °C in a flow of air (30
mL/min) under 5 °C/min heating rates.
2.4. Catalytic Performance Evaluation
Vapor-phase Doebner-Von Miller reaction was performed in the fixed-bed
reactor, and the typical operating process was as follows: firstly, 1.0g of catalyst was
6

Page 7 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
placed in the middle of the stainless steel reaction tuber (i.d. 8mm), and then heated in
nitrogen flow of 30mL/min until reaching reaction temperature. Subsequently, the
feedstocks mixtures, containing aniline(AN) and acrolein acetal(AA), were fed into
the fixed-bed reactor. The products were collected and cooled using ice-water trap.
The product mixtures were analyzed and identified on Varian Saturn 2200/CP-3800
gas chromatography-mass spectrometry, in which two CP8944 capillary columns
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
VF-5, 30m0.25mm0.25m) were equipped and connected to flame ionization
detector and mass detector. The yield of quinoline(Q), methylquinoline(MeQ) and
ethylquinoline(EtQ) were calculated based on the converted acrolein acetal(AA).
moles of AA converted
Conversion (mol%) =
Selectivity (mol%) =
× %
moles of AA input
moles of product
× %
moles of AA converted
Yield (mol%) = Conversion × Selectivity × %
3
3
. Results and Discussions
.1. Catalyst Characterization
The XRD patterns of catalysts are shown in figure 1(a). After crystallization for
2 h, the framework structure of HBeta zeolite is well generated. Interestingly,
1
mordenite phase begin to form in zeolite after recrystallization to 24 h, and more
mordenite phase as well as other additional phase generate in zeolite as further
prolonging crystallization time to 36 h. Several literatures reported that post-synthesis
treatments could induce formation of additional phases.35, 38 It infers that mordenite
phase and other additional phase could be generated from zeolitic fragments as
prolonging recrystallization time. Obviously, the intensity of peaks over HBeta-Ct
decrease than that over HBeta, owing to the decreased relative crystallinity (94.3%) of
HBeta-Ct (table 1S). The small-angle XRD pattern of HBeta-Ct shows no obvious
peak (figure 1S). it indicates that the ordered mesoporous MCM-41 phase was not
formed during the CTAB&NaOH co-treatment process. In addition, the ratio of Si/Al
ratio of HBeta-Ct decreases slightly. This is probably due that some silicon species
7

New Journal of Chemistry
Page 8 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
dissolved in alkali solution and was not assembled to rebuild framework of zeolite. As
a result, 93.4% yield of product is obtained.
Generally, alkaline post-treatment could generate mesopores within zeolite and
also retain main the structure of zeolite, via extracting silicon from framework of
zeolite. The XRD patterns of alkali-treated parent HBeta zeolites with different alkali
concentration are shown in figure 2S. Clearly, parent HBeta zeolites retain partly
framework structure using low-concentration alkali treatment (<0.6 mol/L), while
parent HBeta zeolites structure is destroyed entirely to form amorphous phase at
high-concentration alkali treatment under the same operation condition (> 1.0 mol/L).
this shows that the zeolite structure of HBeta-Ct is not from the retained parent
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
structure of HBeta zeolite through high-concentration alkali treatment. It infers that
the formed amorphous phases consist of zeolitic fragments and even zeolite seeds,38
which favors the following zeolitic reassembling process. It indicates that the forming
zeolite structure of HBeta-Ct is ascribed to the reassembling of amorphous phase.
a
Mordenite
Other phase
b
947
7
97
5
72
524
HBeta-Ct
1
229
HBeta-Ct-36
HBeta-Ct-24
1087
HBeta
HBeta-Ct
HBeta
5
10
15
20
25
30
35
40
45
50
1
400
1200
1000
800
600
400
-1
2
-Theta (degree)
Wavenumber(cm )
Figure 1. the XRD patterns(a) and FT-IR spectra(b) for catalysts
The FT-IR spectras of catalysts are shown in figure 1(b). The bands at ca. 797,
-1
1
087, and 1229 cm are related to the external symmetric, internal asymmetric and
external asymmetric stretching vibrations of tetrahedron units, respectively.39-41
-
1
Moreover, the bands at ca. 524 and 568 cm are presumably attributed to framework
8

Page 9 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
characteristic of Beta zeolite.42,
43
DOI: 10.1039/D0NJ04539J
Obviously, HBeta-Ct zeolite shows good
characteristic vibrations of Beta zeolite, while the bands intensities of HBeta-Ct
zeolite decrease slightly relative to the parent HBeta one. The results further
demonstrate that HBeta-Ct zeolite possesses a good zeolite framework structure but
its crystallinity reduces accordingly.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The HRTEM micrographs of catalysts are shown in figure 2. The parent HBeta
zeolite is free of intracrystalline defects and shows a clear crystal lattice in the
44
framework. This indicates the high crystallinity of parent HBeta zeolite. However,
the HBeta-Ct zeolite presents obvious defects liking irregular cracks. This may be
relating to the generation of mesopores, thereby forming the hierarchical structure.34
In addition, as shown in SEM micrographs (see in figure 3S), the parent HBeta zeolite
consists of many bulk irregular agglomerate crystal grains, but the HBeta-Ct zeolite
shows larger size of crystal grains than the parent HBeta one.
Figure 2. The TEM images of HBeta(a, b) and HBeta-Ct(c, d)
9

New Journal of Chemistry
Page 10 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
The N adsorption-desorption isotherms of catalysts are shown in figure 3(a).
2
The isotherms rise rapidly at low relative pressure over all catalysts, due to the
adsorption of N in micropore. A prominent hysteresis loop is present over the
2
HBeta-Ct zeolite but absent over the parent HBeta one at P/P >0.4. The appearance of
0
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
hysteresis loop further indicates the existence of certain mesopores over HBeta-Ct
zeolite. The specific textural properties of the catalysts are listed detailedly in table 1.
The S , S , S as well as Vmic over the HBeta-Ct zeolite decreases to some extent,
mic
ext
BET
compared to the parent HBeta one. Interestingly, the HBeta-Ct zeolite possesses as
high as 0.61mL/g of mesopore volume, and mesopore size is centered at ca. 3.85 nm.
The result illustrates that zeolitic dissolution-recrystallization successive treatment
generates mesopores approvingly.
4
4
3
3
50
00
50
00
a
T
1
b
HBeta-Ct
HBeta-Ct
2
0
40
60
80
100
250
Pore diameter(Å)
T
2
HBeta-Ct
HBeta
2
1
1
00
50
00
HBeta
5
0
0
0
.0
0.2
0.4
0.6
0.8
1.0
100
200
300
400
o
500
600
Relative pressure /(P/P
0
)
temperature( C)
Figure 3. the N absorption-desorption isotherms(a) and NH -TPD(b) for catalysts
2
3
Table 1. the textural properties of catalysts.
S
S
S
V
V
V
Dmeso
BET
2
ext
2
mic
2
total
3
mic
3
meso
3
Catalyst
(
m /g)
(m /g) (m /g)
168.2
99.1
(cm /g)
0.40
(cm /g)
0.15
(cm /g)
0.25
0.61
(nm)
-
3.85
HBeta
HBeta-Ct
483.7
332.4
315.5
233.2
0.72
0.11
SBET, Sext and Smic refers to specific surface area, external surface area and micropore surface area,
respectively, and SBET = Sext + Smic; Vtotal and Vmic refers to total pore volume and micropore
volume, respectively; Dmeso refers to mesopore size calculated by the BJH method.
The NH -TPD profiles of catalysts are exhibited in figure 3(b), and the detail
3
acidity data are summarized in table 2. Both of zeolites present two desorption peaks
1
0

Page 11 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
evidently in the range 100~200 °C and 450~550 °C. The low-temperature peak is
generally belonging to weak acid sites. The high-temperature peak is responsible for
strong acid sites. Generally, weak acid sites over zeolite are generally associated to
terminal acid silanol groups of zeolite,45, 46 and strong acid sites are assigned to
bridging Si-(OH)-Al group of zeolite. The HBeta-Ct zeolite presents smaller
low-temperature as well as high-temperature peaks than the parent HBeta one. The
result indicates that both weak and strong acid sites decrease slightly over the
HBeta-Ct zeolite, as shown in table 2.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Table 2. the NH -TPD results for catalysts.
3
a
b
T (°C) and A (mmol/g) for various desorption peaks
i
i
Catalyst
T1
A1
T2
A2
Atotal
1.58
1.05
A /A
0.28
0.22
2
1
HBeta
HBeta-Ct
1.23
0.86
0.35
0.19
1
59.6
494.5
a
Ti refers to the temperature at the maximum of desorption peak i.
b
A refers to the integral area of desorption peak i, and it means also the concentration of acid site
i
corresponding to the desorption peak i; Atotal stands for the sum of the concentration of various
acid site, i.e., Atotal =
.
Therefore, the above results demonstrate that, relative to the parent HBeta
zeolite, the reassembled HBeta zeolite via zeolitic dissolution-recrystallization
processes possesses more mesopores and less concentration of weak and strong acid
sites.
3
.2 Catalytic Activity
Vapor-phase Doebner-Von Miller reaction to quinolines is conducted in
fixed-bed reactor, utilizing aniline and acrolein acetals as starting materials. Firstly,
two types of acrolein acetals are employed as feedstock to synthesize quinolines over
the parent HBeta catalyst. As shown in figure 4(a). The experiments results exhibit
that both acrolein dimethyl acetal(AMA) and acrolein diethyl acetal(ADA) are
converted with 100% at high temperature. The products of Q, MeQ and EtQ are
generated distinctly in this reaction. According to previous literatures, it infers that Q,
MeQ and EtQ are generated with ADA as reactant via different paths. As shown in
Eq.(1-5), ADA is firstly hydrolyzed to acrolein and ethanol (Eq. 1). Then, aniline
reacts with acrolein to yield Q via Michael addition-aromatization processes (Eq. 2).47
1
1

New Journal of Chemistry
Page 12 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
Quinoline can further react with ethanol to produce EtQ via alkylation over acid
4
8
sites. Meanwhile, ADA and acrolein can be cracked to generate acetaldehyde over
4
9
solid-acid catalyst at high temperature (Eq. 4). The generated acetaldehyde could
1
6
react with aniline to yield MeQ (Eq. 5). Apparently, total yields of Q (containing Q,
s
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
MeQ and EtQ) increases up to ca. 76% from ca. 60.8% using ADA as feedstock,
compared to AMA using in this reaction. Thus, ADA is utilized as preferred feedstock
in this reaction.
hydrolysis
(
1)
CH =CH-CH(OEt)
H O
CH =CH-CHO
2
EtOH
2
2
2
condensation
Ph-NH2
Q (quinoline)
(
2) CH =CH-CHO
2
alkylation
EtQ (ethylquinoline)
(3) Q
EtOH
cracking
(
4) CH =CH-CH(OEt) / CH =CH-CHO
2
2
2
CH CHO
3
condensation
(
5) 2CH CHO
Ph-NH2
MeQ (Methylquinoline)
3
1
00
100
a
b
Conversion
Conversion
9
0
90
80
70
60
50
40
30
20
10
0
Yield of EtQ
Yield of MeQ
Yield of Q
Yield of EtQ
Yield of MeQ
Yield of Q
80
7
6
5
4
0
0
0
0
30
2
1
0
0
0
acrolein dimethyl acetal acrolein diethyl acetal
HY
HUSY
HZSM-5
HBeta
HBeta-Ct
Feedstock
Catalyst
Figure 4. the effect of feedstocks(a) and various zeolite catalysts(b)
o
Reaction condition: temperature(440 C), ratio of AN/ADA(3:1), LHSV of mixture feedstocks(1.0
-1
-1
h ), LHSV of H O(1.0 h ), reaction time(1 h). Q, MeQ and EtQ refer respectively to quinoline,
2
methylquinoline and ethylquinoline.
As comparison, catalytic activities of different types of zeolites are also tested,
and the catalytic results are shown in figure 4(b). The total yields of Q obtained over
s
catalysts show an order of HBeta > HY > HUSY > HZSM-5. Interestingly, this
sequence of the yield of Q is not consistent with the total acid amount over zeolite
s
(see figure 4S and table 2S). It infers that the catalytic activities are influenced by not
only acid amount but also porous structure of zeolite. For instance, ZSM-5 zeolite
1
2

Page 13 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
may impose diffusion limitation of bulky products because of its small intersected
pore (0.53×0.56 nm and 0.51×0.55 nm). Both of HY and HUSY zeolites could lead to
deep polymerization of products due to its supercages structure. While Beta zeolite
possesses large micropore channel (0.56×0.56 nm and 0.66×0.67 nm), which matches
well with quinolines molecule size. Thus, both of the acidity and porous structure are
responsible for the catalytic activity over various zeolites. Besides, the yield of Q,
MeQ and EtQ decreases slightly over HBeta-Ct catalyst, relative to the parent HBeta
one. Due to acid sites acting as the effective activity sites in DVM reaction to generate
quinolines, the decrease of acid amount over HBeta-Ct reduces the yield of Qs.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
00
100
90
80
70
60
50
40
30
20
10
0
a
Conversion
b
Conversion
9
0
Yield of EtQ
Yield of MeQ
Yield of Q
Yield of EtQ
Yield of MeQ
Yield of Q
80
7
6
0
0
50
4
0
30
2
1
0
0
0
3
80
410
440
470
500
1
2
3
4
o
Temperature / C
Ratio of AN/ADA
100
100
90
80
70
60
50
40
30
20
10
0
c
d
Conversion
Conversion
9
8
7
6
5
4
3
0
0
0
0
0
0
0
Yield of EtQ
Yield of MeQ
Yield of Q
Yield of EtQ
Yield of MeQ
Yield of Q
20
1
0
0
0
.5
0.75
1
1.25
0.25
0.5
0.75
1
1.25
-1
-1
LHSV of Feedstocks /h
LHSV of H O /h
2
Figure 5. the effect of reaction conditions over the HBeta-Ct catalyst
-
1
Reaction condition: Temperature(a): ratio of AN/ADA(3:1), LHSV of mixture feedstocks(1.0 h ),
LHSV of H O(1.0 h ). Ratio of AN/ADA(b): temperature(440 oC), LHSV of mixture
-
1
2
-1
-1
o
feedstocks(1.0 h ), LHSV of H O(1.0 h ). LHSV of mixture feedstocks(c): temperature(440 C),
2
1
3

New Journal of Chemistry
Page 14 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
-
1
o
ratio of AN/ADA(3:1), LHSV of H O(1.0 h ). LHSV of H O(d): temperature(440 C), ratio of
2
2
-1
AN/ADA(3:1), LHSV of mixture feedstocks(1.0 h ).
Reaction influence factors are systematically investigated over HBeta-Ct zeolite.
The effect of temperature is shown in figure 5(a). Total yields of Q are just ca. 55%
s
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
at 380 °C. With elevating temperature, the total yields increase sharply, arriving to ca.
7
6% at 440 °C as its maximum, and then decreases obviously. Generally, relatively
1
7
high temperature favors vapor-phase synthesis of quinolines. Whereas exceeding
450 °C leads to excessive cracking of ADA and polymerization of active
intermedium, thereby decreasing yield of quinolines.
The effect of the ratio of AN/ADA is shown in figure 5(b). Yield of Q and Q
s
increases clearly as increasing AN/ADA ratio, and reaches to its optimum value at
AN/ADA ratio of 3. Generally, elevating ratio of AN/ADA could increase contact
opportunity of reactants, promoting the generation of quinolines. However, too high
ratio of AN/ADA gives rise to alkalescent aniline excessively occupying acid sites of
catalyst, which is bad for reaction process.
The effect of LHSV of mixture feedstocks is shown in figure 5(c). obviously,
-1
yield of Q and Q achieve the highest values at LHSV of 1.0 h . Generally, reducing
s
the LHSV could increase stay time of reactants over catalyst, thereby affecting the
degree of reaction. The reaction is conducted more completely as prolonging stay
time of reactants on the catalyst. Nevertheless, the probability of side reactions, such
as, acrolein polymerization and coking forming, increases with further prolonging
long staying time.
The effect of LHSV of H O is shown in figure 5(d). Obviously, the highest yield
2
-1
of Q as well as Q is obtained at H O LHSV of 1.0 h . In fact, addition of H O into
s
2
2
reactor has notable influence on yield of Q and Q . Because H O feeding into reaction
s
2
system not only facilitates hydrolysis of ADA but also retards acrolein polymerization
and/or other side-reactions via diluting concentration of active intermediate.
Catalyst life of the parent and reassembled HBeta zeolite catalysts are also
evaluated. As the increasing of reaction time, the yield of Q and Q decreases to
s
varying degrees over both of catalysts (figure 6a). Compared to the parent HBeta
1
4

Page 15 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
catalyst, deactivation rate becomes slower distinctly over the HBeta-Ct one (figure
6
a). For instance, as prolonging reaction time to 12 hours, only 28% of relative
catalytic activity is reserved over the parent HBeta catalyst, whereas more than 74%
of relative catalytic activity is remained over the HBeta-Ct one (figure 7b). Therefore,
the result demonstrates that the HBeta-Ct catalyst exhibits stronger ability to inhibit
deactivation than the parent HBeta one. On one hand, the existence of mesoporous
over HBeta-Ct zeolite reduces diffusional limitation of bulky products. On the other
hand, the decreasing of acid amount (especially strong acid sites) over HBeta-Ct
zeolite restrains the acid-induced polymerization side reactions. As a result, the
HBeta-Ct catalyst could accelerate the leaving of products (liking quinolines) from
pore channels in zeolite and restrict the formation and deposition of the coking in pore
channels of catalyst.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
00
90
80
70
1.2
1.1
1.0
100
b
Conversion
a
9
8
7
6
0
0
0
0
HBeta-Ct
Yield of Q over HBeta
Yield of Q over HBeta-Ct
Yield of Qs over HBeta
Yield of Qs over HBeta-Ct
0
.9
HBeta
0.8
0.7
0.6
6
5
4
3
0
0
0
0
50
4
3
0
0
0
0
0
0
.5
.4
.3
.2
HBeta
20
20
10
0
1
0
0
HBeta-Ct
1
2
3
4
5
6
7
8
9
10 11 12
1
2
3
4
5
6
7
8
9
10 11 12
Time on stream /h
Time on stream /h
Figure 6. catalyst life of the HBeta and HBeta-Ct catalysts
o
Reaction condition: temperature(440 C), ratio of AN/ADA(3:1), LHSV of mixture feedstocks(1.0
-
1
-1
h ), LHSV of H O(1.0 h ). Relative catalytic activity was estimated via the yield of Q
2
s(different time)
divided that of Qs(the first hour)
)
On the basis of EtQ generating from alkylation of Q with ethanol, as shown in
Eq.(1-5), the ratio value of EtQ/(EtQ+Q) could be considered to reflect alkylation
degree of Q to EtQ; i.e. the smaller the ratio value, the lower the alkylation degree.
Obviously, the ratio value of EtQ/(EtQ+Q) over HBeta-Ct is lower than that over
HBeta at each same time nodes (figure 6b). It indicates that the HBeta-Ct catalyst
sharply retards alkylation process, which exhibits better ability of anti-alkylation than
1
5

New Journal of Chemistry
Page 16 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
the HBeta one. This is possibly due to more mesopores as well as lower acid sites
amount over HBeta-Ct zeolite than that over the HBeta one. Because the existence of
mesoporous strengthen the diffusion of Q from the internal of catalysts and then
decrease the probability of alkylation of Q with ethanol. Meanwhile, the lower acid
amount over HBeta-Ct could also decrease the alkylation processes. Besides, this ratio
value of EtQ/(EtQ+Q) rises obviously over both of catalyst, as prolonging reaction
time (figure 6b). This shows that, with the increasing of reaction time, the alkylation
increases clearly. Therefore, the result indicates that the HBeta-Ct catalyst could not
only enhance the stability of catalyst significantly but also restrict the alkylation
process distinctly.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The regenerability of the HBeta and HBeta-Ct catalysts is shown in figure 7.
Apparently, catalytic activities of the deactivated HBeta and HBeta-Ct catalysts are
resumed almost completely, after calcining straightforwardly at 550 C in air for 4 h. It
suggests that both of catalyst exhibits a good regenerability. The deactivation is
possible due to the deposition of coking on internal surface of catalyst. Because the
coking on catalysts can be easily removed via calcining at 550 C in air for 4 h, and
catalytic activity of both catalysts are almost fully recovered. In addition, the
thermogravimetric measurements of deactivated catalysts are shown in figure 4S. The
loss of weight at 345~700 °C should arise from the combustion of the coking.
Obviously, the HBeta-Ct zeolite catalyst shows lower loss rate of weight, indicating
stronger ability of anti-coking in DVM reaction.
1
00
Conversion
9
0
fresh
regeneration
regeneration
80
7
6
5
0
0
0
40
3
2
1
0
0
0
0
HBeta
HBeta-Ct
0
3
6
9
12
15
18
21
24
27
30
33
36
Reaction time /h
1
6

Page 17 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ04539J
Figure 7. the regenerability of the HBeta and HBeta-Ct catalysts
Reaction condition: temperature(440 oC), ratio of AN/ADA(3:1), LHSV of mixture
-1
-1
feedstocks(1.0 h ), LHSV of H O(1.0 h ). The deactivated catalysts were regenerated via
2
o
calcining at 550 C in air for 4 h.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4．Conclusions
Mesoporous HBeta-Ct zeolite was prepared by means of zeolitic
dissolution-recrystallization successive processes, and used as the green and efficient
solid-acid catalyst for vapor-phase Doebner-Von Miller reaction to quinolines. The
HBeta-Ct zeolite possessed more mesopores but less acidic concentration, which
exhibited higher selectivity of Q, better ability of anti-alkylation and enhanced
stability of catalyst, relative to the HBeta one. This is presumably due to the
existence of mesopores as well as the decrease of strong acid sites over the HBeta-Ct
zeolite, which could improve diffusion limitation of products, decrease the alkylation
of Q as well as retard deposition of the coking. Besides, the HBeta-Ct catalysts also
exhibited good regenerability in Doebner-Von Miller reaction.
Acknowledgments
This work was supported by the National Natural Science Foundation of China
(
No. 51978648 and 51804116), the Hunan Provincial Natural Science Foundation of
China (No. 2019JJ50215).
References
[
1] M. Ramanathan, J. Wan, Y.-H. Liu, S.-M. Peng and S.-T. Liu, Org. Biomol. Chem., 2020, 18,
75-982.
9
[
[
[
[
2] J. Xu, Q. Chen, Z. Luo, X. Tang and J. Zhao, RSC Adv., 2019, 9, 28764-28767.
3] L. Yang and J.-P. Wan, Green Chem., 2020, 22, 3074-3078.
4] C. M. Leir, J. Org. Chem., 1977, 42, 911-913.
5] Y. Kobayashi, J. Igarashi, C. Feng, Toshifumi and Tojo, Tetrahedron Lett., 2012, 53, 3742-3745.
[6] G. A. Ramann and B. J. Cowen, Tetrahedron Lett., 2015, 56, 6436-6439.
[
[
7] A. Carral-Menoyo, N. Sotomayor and E. Lete, Catal. Sci. Technol., 2020, 10, 5345-5361.
8] A. Das, N. Anbu, P. Varalakshmi, A. Dhakshinamoorthy and S. Biswas, New J. Chem., 2020, 44,
10982-10988.
[
9] H. Vuong, M. R. Stentzel and D. A. Klumpp, Tetrahedron Lett., 2020, 61, 151630.
1
7

New Journal of Chemistry
Page 18 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
[
[
10] X. Zhou, Z. Qi, S. Yu, L. Kong, Y. Li, W.-F. Tian and X. Li, Adv. Synth. Catal., 2017, 359, 1620-1625.
11] G. S. Kumar, P. Kumar and M. Kapur, Org. Lett., 2017, 19, 2494-2497.
[12] A. B. Halgeri and J. Das, Appl. Catal., A, 1999, 181, 347-354.
[
[
13] N. Katada, Y. Kageyama, K. Takahara, T. Kanai, H. Ara Begum and M. Niwa, J. Mol. Catal. A:
Chem., 2004, 211, 119-130.
14] D. H. Choo, H. J. Kim, B. H. Kong, I. S. Choi, Y. C. Ko, H. C. Lee, J. C. Kim and J. S. Lee, J. Catal.,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
002, 207, 183-193.
[
[
15] K. Hensen, C. Mahaim and W. F. HiSlderich, Appl. Catal., A, 1997, 149, 311-329
16] R. Brosius, D. Gammon, F. Vanlaar, E. Vansteen, B. Sels and P. Jacobs, J. Catal., 2006, 239,
362-368.
[
[
17] A. Li, C. Huang, C. W. Luo, W. J. Yi and Z. S. Chao, RSC Adv., 2017, 7, 9551-9561.
18] A. Li, C. Huang, C.-W. Luo, L.-J. Li, W.-J. Yi, T.-W. Liu and Z.-S. Chao, Catal. Commun., 2017, 98,
13-16.
[
[
[
19] A. Li, C. Luo, Y. Liu, L. Li, Y. Lin, K. Liu and C. Zhou, Molecular Catalysis, 2020, 486, 110833.
20] J. Jin, X. Ye, Y. Li, Y. Wang, L. Li, J. Gu, W. Zhao and J. Shi, Dalton Trans., 2014, 43, 8196-8204.
21] C. Yin, D. Tian, M. Xu, Y. Wei, X. Bao, Y. Chen and F. Wang, J. Colloid Interf. Sci, 2013, 397,
1
08-113.
22] F. Tian, Y. Wu, Q. Shen, X. Li, Y. Chen and C. Meng, Microporous Mesoporous Mater., 2013, 173,
29-138.
[23] Y. Wu, F. Tian, J. Liu, D. Song, C. Jia and Y. Chen, Microporous Mesoporous Mater., 2012, 162,
68-174.
24] F. Tian, X. Yang, Y. Shi, C. Jia and Y. Chen, J. Nat. Gas Chem., 2012, 21, 647-652.
[
1
1
[
[25] K. Cheng, J. Kang, S. Huang, Z. You, Q. Zhang, J. Ding, W. Hua, Y. Lou, W. Deng and Y. Wang, ACS
Catal., 2012, 2, 441-449.
[
[
26] H. Yang, Z. Liu, H. Gao and Z. Xie, Appl. Catal., A, 2010, 379, 166-171.
27] J. Zhu, Y. Zhu, L. Zhu, M. Rigutto, A. van der Made, C. Yang, S. Pan, L. Wang, L. Zhu, Y. Jin, Q. Sun,
Q. Wu, X. Meng, D. Zhang, Y. Han, J. Li, Y. Chu, A. Zheng, S. Qiu, X. Zheng and F. S. Xiao, J. Am.
Chem. Soc., 2014, 136, 2503-2510.
[
28] A. Ishihara, K. Inui, T. Hashimoto and H. Nasu, J. Catal., 2012, 295, 81-90.
[29] K. Moller, B. Yilmaz, R. M. Jacubinas, U. Muller and T. Bein, J Am Chem Soc, 2011, 133,
284-5295.
30] H. Zhang and Y. Li, Powder Technol., 2008, 183, 73-78.
[31] Y. Tong, T. Zhao, F. Li and Y. Wang, Chem. Mater., 2006, 18, 4218-4220.
5
[
[
32] S. Bernasconi, J. A. van Bokhoven, F. Krumeich, G. D. Pirngruber and R. Prins, Microporous
Mesoporous Mater., 2003, 66, 21-26.
[
[
33] W. Guo, C. Xiong, L. Huang and Q. Li, J. Mater. Chem., 2001, 11, 1886-1890.
34] N. Suárez, J. Pérez-Pariente, F. Mondragón and A. Moreno, Microporous Mesoporous Mater.,
2
019, 280, 144-150.
[
35] K. Zhang, S. Fernandez, S. Kobaslija, T. Pilyugina, J. O’Brien, J. A. Lawrence and M. L. Ostraat, Ind.
Eng. Chem. Res., 2016, 55, 8567-8575.
[
[
36] A. Karlsson, M. Stöcker and R. Schmidt, Microporous Mesoporous Mater., 1999, 27, 181-192.
37] H. Li, H. Wu and J.-l. Shi, J. Alloy. Compd., 2013, 556, 71-78.
[38] I. I. Ivanova and E. E. Knyazeva, Chem. Soc. Rev., 2013, 42, 3671-3688.
39] A. Vimont, F. Thibault-Starzyk and J. C. Lavalley, J. Phys. Chem. B, 2000, 104, 286-291.
[
1
8

Page 19 of 20
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
[
40] I. Othman, R. M. Mohamed, I. A. Ibrahim and M. M. Mohamed, Appl. Catal., A, 2006, 299,
DOI: 10.1039/D0NJ04539J
9
5-102.
[41] L. Shirazi, E. Jamshidi and M. R. Ghasemi, Cryst. Res. Technol., 2008, 43, 1300-1306.
[
[
42] J. Perez-Pariente, J. A. Martens and P. A. Jacobs, Appl. Catal., 1987, 31, 35-64.
43] I. Kiricsi, C. Flego, G. Pazzuconi, W. O. Parker, Jr., R. Millini, C. Perego and G. Bellussi, J. Phys.
Chem., 1994, 98, 4627-4634.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
[
[
[
44] H. Yang, P. Yang, X. Liu and Y. Wang, Chem. Eng. J., 2016, 299, 112-119.
45] Y. T. Kim, K. D. Jung and E. D. Park, Microporous Mesoporous Mater., 2010, 131, 28-36.
46] B. O. D. Costa, M. A. Peralta and C. A. Querini, Appl. Catal., A, 2014, 472, 53-63.
[47] B. M. Reddy and I. Ganesh, J. Mol. Catal. A: Chem., 2000, 151, 289-293.
[
[
48] P. R. Reddy, K. V. S. Rao and M. Subrahmanyam, Catal. Lett., 1998, 56, 155-158.
49] L. Shen, H. Yin, A. Wang, Y. Feng, Y. Shen, Z. Wu and T. Jiang, Chem. Eng. J., 2012, 180, 277-283.
1
9

New Journal of Chemistry
Page 20 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ04539J
Graphical Abstract
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Mesoporous HBeta zeolite was obtained via zeolitic dissolution-recrystallization successive
treatment, which exhibited higher selectivity of Q, better ability of anti-alkylation as well as
catalyst stability in vapor-phase Doebner-Von Miller reaction, relative to the HBeta one.